Chiral phosphinite-boranes and their preparation and use

Details Chiral phosphinite-boranes and their preparation and use Chiral phosphinite-boranes and their preparation and use

1993-10-07

1995-07-18

Richter, Johann

Organic compounds -- part of the class 532-570 series

Organic compounds

Silicon containing

C07F 702

Patent

active

054342856

DESCRIPTION:

BRIEF SUMMARY
This application is a 371 of PCT/FR92/00143, filed Feb. 13, 1992.
1. Field of the Invention
The present invention relates to a novel class of phosphinite compounds, especially chiral phosphinite compounds. It relates more precisely to the phosphinite-borane compounds of formula I.sub.o below, in which the two phosphorus atoms are both complexed by (or bonded to) a borane group. These phosphinite-borane compounds carry one or more labile or substitutable groups permitting nucleophilic substitution, for example by an alkylating, cycloalkylating or arylating group.
The present invention further relates to the methods of preparing these phosphinite-borane compounds and to their uses in the preparation of diphosphines.
2. Prior Art
It is known that phosphinite compounds, and particularly those which are optically active, are industrially useful both per se and as starting materials for the preparation of other useful chiral products such as, in particular, phosphine oxides, phosphines, etc.
Numerous natural and synthetic products can now be prepared by asymmetric synthesis catalyzed by means of transition metals, and especially with catalysts containing optically active organophosphorus ligands. The asymmetric synthesis route makes it possible to obtain substances which are of value in the fields of agriculture, food, pharmacy or perfumery. Known examples illustrating said asymmetric synthesis route are the production of L-dopa, L-phenylalanine, menthol or citronellol.
The preparation of two compounds of the formula ##STR2## in which R.sup.A is ortho-anisyl or 2-naphthyl, is known from an article by the co-inventors of the present invention, namely S. JUGE et al., Tetrahedron Letters 31(no. 44) pages 6357-6360 (1990). The two compounds of formula I.sub.A according to scheme 2 in said article (see page 6358) are obtained from ##STR3## (in which R.sup.A is defined as indicated above and R.sup.B is CH.sub.3) by the reaction of two mol of I.sub.B with (i) s-BuLi, then (ii) CuCl.sub.2.
Said article, which is incorporated here by way of reference, also describes formula ##STR4##
In another connection, two products of formula I.sub.o, namely the compound in which R.sup.1 =Ph, R.sup.2 =Me R.sup.3 =Me and Z=CH.sub.2 and, respectively, the compound in which R.sup.1 =Ph, R.sup.2 =Me, R.sup.3 =MeO and Z=CH.sub.2 CH.sub.2, are known from Examples 21 and 22 of published PCT international patent application WO 91/00286 (publication date: 10th January 1991).


OBJECT OF THE INVENTION

One object of the invention is to provide novel phosphinite-borane compounds which are structurally different from those of the prior art cited above.
Another object of the invention is to provide a general method of preparing the novel compounds of formula I.sub.o below, and specific methods of preparing these compounds.


SUBJECT OF THE INVENTION

According to a first feature of the invention, a novel phosphinite compound substituted by BH.sub.3 on the phosphorus is provided which is selected from the group consisting of the phosphinite-borane products of the general formula ##STR5## in which R.sup.1 and R.sup.2, which are identical or different, are each a C.sub.1 -C.sub.18 -alkyl group, a C.sub.5 -C.sub.18 -cycloalkyl group, a C.sub.7 -C.sub.18 -aralkyl group or a C.sub.6 -C.sub.14 -aryl group, it being possible for each of these groups to carry functional groups, C.sub.7 -C.sub.18 -aralkyl, C.sub.6 -C.sub.14 -aryl, C.sub.1 -C.sub.18 -alkoxy, C.sub.7 -C.sub.18 -cycloalkoxy, C.sub.7 -C.sub.18 -aralkoxy or C.sub.6 -C.sub.14 -aryloxy group, and hydrocarbon chain having from 1 to 12 catenary C atoms, or (ii) a heterohydrocarbon chain containing from 1 to 12 catenary C atoms and at least one catenary heteroatom selected from O, S, Si, P and N, =phenyl and R.sup.2 =R.sup.3 =methyl simultaneously, and (ii) Z is other than CH.sub.2 CH.sub.2 when R.sup.1 =phenyl, R.sup.2 =methyl and R.sup.3 =methoxy simultaneously.
From a chiral point of view, a compound of formula I.sub.o can be represented by the following structure: ##STR6## where R.sup.1, R.sup.2,

REFERENCES:
patent: 5264602 (1993-11-01), Juge et al.
S. Juge et al., "Efficient asymetric synthesis of optically pure tertary mono and diphosphine Ligands", Tetrahedron Letters, vol. 31, No. 44, 1990, Oxford, Great Britain, pp. 6357-6360.

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